Synergistic chrysanthemate insecticides

ABSTRACT

An insecticidal composition containing an inert carrier and as active ingredients an insecticidally effective amount of a mixture consisting of N-(3,4,5,6-tetrahydrophthalimido)-methyl chrysanthemate or 2-allyl-3-methyl-cyclopent-2-ene-1-one-4-yl chrysanthemate and 3-phenoxybenzyl-2&#39;&#39;,2&#39;&#39;-dimethyl-3&#39;&#39;-(2&#39;&#39;&#39;&#39;,2&#39;&#39;&#39;&#39;dichlorovinyl) cyclopropanecarboxylate, which has low toxicity to mammals and excellent in both knock-down and killing effects.

United States Patent [191 Okuno et al.

[ SYNERGISTIC CHRYSANTHEMATE INSECTICIDES [75] Inventors: YoshitoshiOkuno, Toyonaka;

Masachika I-Iirano, Ashiya, both of Japan [73] Assignee: SumitomoChemical Company,

Limited, Osaka, Japan 22 Filed: 00:. 16,1974

21 Appl. No.: 515,332

[30] Foreign Application Priority Data Aug. 12, 1975 3,402,179 9/1968Fujimoto et a1. 424/306 X 3,723,615 3/1973 Okuno 424/306 X 3,792,0792/1974 DOkazio et al 424/306 X FOREIGN PATENTS OR APPLICATIONS 7,307,1301 H1973 Netherlands Primary Examiner-Albert T. Meyers AssistantExaminerLeonard Schenkman Attorney, Agent, or Firm-Stevens, Davis,Miller & Mosher ABSTRACT An insecticidal composition containing an inertcarrier and as active ingredients an insecticidally effective amount ofa mixture consisting of N-(3,4,5,6-tetrahydrophthalimido)-methylchrysanthemate or 2-allyl-3- rnethyl-cyclopent-Z-enel -one-4-ylchrysanthemate and 3-phenoxybenzyl-2 ',2 -dimethyl-3 2 ',2dichlorovinyl) cyclopropanecarboxylate, which has low toxicity tomammals and excellent in both knockdown and killing effects.

9 Claims, 3 Drawing Figures PATENTEDAUGIZIHYB 3,899,585

FIG. I

RELATION BETWEEN MIXING RATIO OF (iI-TRANS BODIES OF COMPOUNDNOS.(|)ANO(3)AND KNOCK-DOWN RATIO OR MORTALITY KNOCK-DOWN RATIOMORTALITY KNOCK-DOWN ATIO MORTALITY (%I O COMPOUND( I I IO COMPOUNDI3) 0MIXING RATIO I PATENTEI] AUG I 2 I975 (HITCT unLLl FIG. 2

RELATION BETWEEN MIXING RATIO OF (H-LON- (+ITRANSBODY OF COMPOUNDIZI AND(iI-CIS. TRANS-BODY OF COMPOUND I3).AND KNOCK-DOWN RATIO OR MORTALITYKNOCK-DOWN RATIO ---x- MORTALITY 95m zaooiuozx MIXING RATIO COMPOUND (2)IO COMPOUND (3) O PATENTEB AUG I 2 I975 SHEET 3 [IF 3 FIG. 3

RELATION BETWEEN MIXING RATIO OFI+I-LON-I+I- TRANS-BODY OF COMPOUNDIZIANDIiI-CIS. TRANS-BODY OF COMPOUNDI3I. AND KNOCK- DOWN RATIO ORMORTALITY KNOCK DOWN RATIO --x MORTALITY Z300 xuozx COMPOUND (2) IOCOMPOUND (3) 0 MIXING RATIO SYNERGISTIC CI-IRYSANTI-IEMATE INSECTICIDESThis invention relates to a novel insecticidal composition containing asactive ingredients N-(3,4,5,6- tetrahydrophthalimido)-methylchrysanthemate [hereinafter referred to as the compound (1)] which is aknown chrysanthemic acid ester type insecticide, or 2-allyl-3-methyl-cyclopent-2-enel -one-4-yl Chrysanthemate [hereinafterreferred to as the compound (2)] which is a known chrysanthemic acidester type insecticide of allethrolon, and, in admixture therewith, 3-phenoxybenzyl-2 ,2 -dimethyl-3 -(2 ,2 dichlorovinyl)cyclopropanecarboxylate [hereinafter referred to as the compound (3)].The composition of the present invention, which is prepared by mixingthe above-mentioned compounds with each other, is extremely high ininsecticidal effect since the demerits of the individual compounds havemutually been filled up due to mixing and the effects thereof havesynergistically been increased.

The compound (1) or (2) is a currently available insecticide whichdisplays an extremely quick knockdown effect against sanitary injuriousinsects such as houseflies, mosquitoes and cockroaches, and agricultureinjurious insects such as green rice leafhoppers, and is most quick inknock-down effect among natural and synthetic chrysanthemic acid estertype compounds. However, the said compound, when used singly, is notalways high in killing effect and hence is sometimes required to beincorporated with a piperonyl butoxide synergist or an insecticide highin killing effect.

The present inventors conducted extensive studies with an aim to coverthe demerits of the compound (I) or (2) while maintaining the meritsthereof. As a result, the inventors have found that when the compound(I) or (2) is mixed with a proper amount of the compound (3), theresulting mixture not only shows a synergistic insecticidal activity todisplay such a surprising effect as not to be anticipated from theeffects of the individual compounds but also is so low in activity as tobe practically usable. Based on the above finding, the inventors haveaccomplished the present invention.

The synergistic effect attained by the mixing of the aforesaid compoundsis explained below with reference to experimental examples. It isneedless to say that the compounds (1), (2) and (3) include theirisomers derived from the acid components thereof.

In the accompanying drawings,

FIG. 1 is a graph showing, in terms of the relation between mixingratio, knock-down ratio and mortality, the effect on housefly adults ofa mixed insecticide comprising the (i)-trans bodies of the compounds (1)and FIG. 2 is a graph showing, in terms of the relation between mixingratio, knock-down ratio and mortality, the effect on housefly adults ofa mixed insecticide comprising a (i)-allethrolon(+)-trans-acid body ofthe compound (2) and a (i)-cis,-trans body of the compound (3); and

FIG. 3 is a graph showing, in terms of the relation between mixingratio, knock-down ratio and mortality, the effect on housefly adults ofa mixed insecticide comprising a (+)-allethrolon-(+)-trans body of the 7compound (2) and a (i)-cis,trans body of the com pound (3).

EXPERIMENTAL EXAMPLE 1 The compounds and mixtures thereof shown in Tablel were individually formulated by use of deodorized kerosene into 0.1%oil preparations. 7

About 50 housefly adults were released in a glass chamber of cm) andthen sprayed with 0.7 ml. of each of the above-mentioned oilpreparations under a pressure of 1.5 kg/cm by use of a glass atomizer.Thereafter, the number of knocked down houseflies was counted tocalculate the value of KT (50% knockdown time). After 10 minutes, theknocked down houseflies were collected and allowed to stand for a day inan observation cage with feeding, and then the number of alive and deadhouseflies was counted to calculate the mortality. The results obtainedwere as set forth in Table 1.

As is clear from Table 1 shown above and from FIG. 1, the mixtures ofthe compounds (1) and (3), particularly the 9:1 to 2:8 mixtures, areexcellent in synergistic effect.

EXPERIMENTAL EXAMPLE 2 The compounds and mixtures thereof shown in Table2 were individually formulated by use of deodorized kerosene into 0.2%oil preparations.

About 50 housefly adults were released in a glass chamber of (70 cm) andthen sprayed with 0.7 ml. of each of the above-mentioned oilpreparations under a pressure of 1.5 kg/cm by use of a glass atomizer.Thereafter, the number of knocked down houseflies was counted tocalculate the value of KT After 10 minutes, the knocked down houseflieswere collected and allowed to stand for a day in an observation cagewith feeding, and then the number of alive and dead houseflies wascounted to calculate the mortality. The results obtained were as setforth in Table 2.

Table 2 Knock-down effect 0.2% Oil preparation KT (sec) Ratio ofMortality effect (:)-Allethrolon-(:)-trans-acid body (hereinafterreferred to as (i)-lon-(+)-trans body) of 125 23 compound (2)(i)-Allethrolon(+)-trans-acid body (hereinafter referred to as(+)-lon-(+)-trans body") of 82 153 36 compound 2) Table 2 ContinuedKnock-down effect 0.2% Oil preparation KT (sec) Ratio of Mortalityeffect (i)-Cis trans-acid body (hereinafter referred 447 28 75 to as(1)-cis,trans body) of compound (3) (i)-Lon-(i)-trans body of compound(2) (i)- (9:1) 102 123 64 Cis,trans body of compound (3) v (8:2) 98 12890 (5:5) 127 98 98 (2:8) 212 59 95 1:9) 291 43 87 (+)-Lon-(+)-tra.nsbody of compound (2) (i)- (9:1) 66 190 75 Cis,trans body of compound (3)(8:2) 67 187 93 (+)-Lon-(+)-trans body of compound (2) (i) (5:5) 83 151100 Cis,trans body of compound (3) As is clear from the accompanyingFIGS. 2 and 3, the lines of knock-down ratio and mortality of mixturesare above the straight line between respective compounds. This meansthat the mixtures show synergistic effect.

EXPERIMENTAL EXAMPLE 3 (+)-Trans body of the compound l (i)-trans bodyof the compound (3) and the mixtures thereof shown in Table 3 wereindividually formulated by use of acetone into test chemicals. The testchemicals were tested in insecticidal effect according to topicalapplication method by dropping a trace amount of each of the chemicalsonto dorsum prothoraxes of German cock- Table 4 roach adults by use of amicrosyn'nge. As the result the E l ifi bl u-at KT 50% lethal doses (LDof the chemicals after 72 hours mu S a e'concen e mmm) were as set forthin Table 3. (i)-Cis,trans body of compound (1) 14' compound (3) 23 Table3 (3:)-Cis,trans body of compound (1) (:)'Cis,trans body of compound (3)(8:2) 13' 5:5 17'. LDM Ratio of (2:8) 17' 30" Test chemical ('y/Roach)effect (+)-Trans body of EXPERIMENTAL EXAMPLE 5 compound (1) 2.43 100 zgy of 0 57 4 (i)-Lon-(+)-trans body of the compound (2), (i)- 311%; g ofO cis,trans body of the compound (3), (+)-trans body of compound 1) 9:1)1.32 184 the compound (3) and the mixtures thereof shown in gi s zz gTable 5 were individually formulated in the same man- (8:2) 1.05 231 neras in Formulation Example 4 described later into (5:5) 0.61 398 (2:8)046 528 aerosol preparations having such active indgredlent H (1.9) 0 59412 concentrations as shown in Table 5. Pyrethn'n L40 174 The aerosolpreparations were tested in insecticidal EXPERIMENTAL EXAMPLE 4L)-Cis,trans bodies of the compounds (1) and (3) 5 and the mixturesthereof shown in Table 4 were indieffect according to the aerosol testmethod [described in Soap & Chemical Specialities, Bluebook (1965)],using a Peet Gradys chamber in which had been released a group of 100housefly adults. The results obtained were as set forth in Table 5.

Table 5 Sprayed Knock-down ratio KT (min) amount Morta- Aerosol g/1000 5min 10 min 15 min Mea- Theorelity ft") sured tical 1 (i)-Llon(+)-transbody of 0.3% 3.2 15 31 56 13.8 12 compound (2) (1)-cis,trans body of0.3% 3.2 4 22 53 14.8 52 compound (3) (+)-Trans body of 0.3% 3.1 9 30 6712.4 76 compound (3) (i)-Lon-(+)-trans body of 0.2% compound (2) 3.2 2264 81 8.0 14.1 85 (i)-Cis,trans body of 0.1% compound (3)(i)-Lon-(+)-trans body of 0.2% compound (2) -3.1 28 79 92 6.6 13.3 95(+)-Trans body of 0.1%

compound (3) 1 :Theoretical value calculated according to thesynergistic effect calculation formula ofYun-Pei Sun et a1. (.1. E. E.,53. pages 887-891 (1960)].

EXPERIMENTAL EXAMPLE 6 (i)-Lon-(+)-trans body of the compound (2),(+)-lon-(+)-trans body of the compound (2), (i)-cis,-

elapsed minutes after being sprayed, were allowed to stand for 3 dayswith feeding in a feeding dish, and the number of alive and deadcockroaches was counted to calculate the mortality. The results obtainedwere as trans body of the compound (3) and the mixtures 5 set forth inTable 6.

Table 6 Sprayed Knock-down ratio KT min) Morta- Aerosol amount Mea-Theorelity (g/0.Om 2.5 5' 10' 20 sured tical*l (i)Lon-(+)-trans body ofcompound (2) 0.3% 0.51 16 38 62 84 7.1 (+)-Lon(+)-trans body of compound(2) 0.3% 0.50 25 53 84 96 4.6 54 (:)-Cis,trar|s body of compound (3)0.3% 0.51 0 9 32 75 13 92 (:t)-Lon-(+)trans body of compound (2) 0.15%(t)-Cis,trans body of V compound (3) 0.15% 0.50 21 45 70 90 5.7 9.2 100(+)-Lon-(+)-trans body of compound (2) 0.15% (i)-Cis,trans body ofcompound (3) 0.15% 0.50 33 62 92 100 3.6 6.8 100 *lzSame as mentionedpreviously.

thereof shown in Table 6 were individually formulated in the same manneras in Formulation Example 14 described later into aerosol preparationshaving such active ingredient concentrations as shown in Table 6.

A glass cylinder of 20 cm in diameter and 20 cm in height was covered atthe bottom with a 16-mesh nylon net and coated with butter at the upperpart of the 35 in diameter and cm in height was further piled on 40 saidcylinder having the cockroaches released therein.

From the top of the thus piled glass cylinder, each of the aforesaidaerosol preparations was sprayed to the cockroaches, and the number ofcockroaches knocked down within 20 minutes was counted with time tocalculate the value of KT The cockroaches, when EXPERIMENTAL EXAMPLE 7(i)-Lon-(+)-cis,trans body of the compound (2), (+)-lon-(+)-cis,transbody of the compound (2), (i)- eis,trans body of the compound (3) andthe mixtures thereof shown in Table 7 were individually formulated inthe same manner as in Formulation Example 6 described later intomosquito coils having such active ingredient contents as shown in Table7.

A group of 25 adults of Northern house mosquitoes was released in eachof four cylindrical cages made of nylon net of 30 cm in diameter and 30cm in height. These cages were individually placed at four corners in a(28 m) chamber and each of the aforesaid mosquito coils was ignited andplaced at the center of the chamber. Subsequently, the number ofmosquitoes knocked down within 2 hours was counted with time tocalculate the value of KT The results obtained were as set forth inTable 7.

Table 7 Knock-down ratio KT (min) Mosquito coil Mea- Theme 15 30 45' 90105 120 sured tical* 1 (:)-Lon-(+)-cis,trans body of compound (2) 0.3% 321 42 59 74 83 88 51 (+)-Lon-(+)-cis,trans body of compound (2) 0.3% 1037 55 72 87 93 97 39 (:)-Cis,trans body of compound (3) 0.3% 0 5 13 3037 48 72 81 87 (i)'Lon-(+)cis,tra.ns body of compound (2) 0.2%(i)-Cis,trans body of compound (3) 0.1% 5 32 58 70 83 94 96 41 59.1(+)-Lon-(+)-cis,trans body of compound (2) 0.2% (:)-Cis,trans body ofcom und (3) 0.1% 19 51 69 81 89 93 96 97 29.5 47.7 on-(+)-cis,trans bodyof compound (2) 0.15% (i)-Cis,trans body of compound (3) 0.15% 15 43 6179 83 90 92 95 34 53.7

' 1 :Same as mentioned previously.

As is clear from the above-mentioned Experimental Examples 1 to 7, themixed insecticides of the present invention are markedly high in tosynergistic effect. I

cides, like in the case of conventional pyrethroids, in

secticidal compositions of optional fOrrns such as oil insecticidal,effect due,

preparations, -emulsifiable concentrates, dust preparations, aerosols,wettable powders, finegranule preparations, mosquito coils, electricalmosquito killer mats,

fogging mists, heating or non-heating fumigant's, and

dust or solid preparation incorporated with baits .or the likesubstances attractive to insects.

The mixed insecticides of the present invention can be enhanced ininsecticidal effect when used in admixture with such synergits forpyrehroids as a-[2-(2- butoxyethoxy )ethoxy -4,5-methylenedioxy-2-propyltoluene (hereinafter referred to as piperonyl butoxide 1,2-methylenedioxy-4-[ 2-(octylsu1finyl)- propyl]benzene (hereinafterreferred to as sulfoxide 4-( 3 ,4-methylenedioxyphenyl )-5-methyl-l ,3-dioxane (hereinafter referred to as Sufroxane), N- (2-ethy1hexyl)-bicyclo 2,2,1 hepta-5-ene-2,3- dicarboximide (hereinafter referred toas MGK- 264), octachlorodipropyl ether (hereinafter referred to as S-42land isobornyl thiocyanoacetate (hereinafter referred to as Thanite), orwith other known synergists effective for allethrin and pyrethrin.

Generally, chrysanthemic acid ester type compounds are somewhat low instability to light, heat and oxidation. Accordingly, when antioxidantsor ultraviolet absorbers, e.g. phenol derivatives such as BHT (butylatedhydroxytoluene) and BHA (butylated hydroxyanisole), bisphenolderivatives, arylamines such as phenyl-anaphthylamine,phenyl-B-naphthylamine and phenetidine condensates, or benzophenone typecompounds are added in suitable amounts as stabilizers to the mixedinsecticides of the present invention, it is possible to obtaininsecticidal compositions which have been more stabilized ineffectiveness.

Furthermore, the mixed insecticides of the present invention may be usedin admixture with physiologically active substances, e.g.organo-chlorine type insecticides such as DDT, BHC and methoxychlor;organo-phosphorus type insecticides such as 0,0- dimethyl-O-(3-methyl-4-nitrophenyl )phosphorothioate [hereinafter referred to asSumithion (registered trademark of Sumitomo Chemical Co., Ltd.)], 0,0-dimethyl-O-(2,2-dichlorovinyl) phosphate (hereinafter referred to asDDVP) and 0,0-dimethyl-O-4- cyanophenyl phosphorothioate [hereinafterreferred to as Cyanox (registered trademark of Sumitomo Chemical Co.,Ltd.)]; carbamate type insecticides such as l-naphthyl-N-methylcarbamate, 3,4-dimethylphenyl-N-methyl carbamate, 3 ,5-dimethylphenyl-N-methyl carbamate and 2-isopropoxyphenyl-N-methyl carbamate;chrysanthemic acid ester type insecticides such as known chrysanthemicacid esters and their isomers, or other insecticides, or with otheragricultural chemicals such as fungicides, nematocides, acaricides,herbicides, fertilizers, microbial pesticides such as BT preparationsand BM preparations, and insect hormones, 7 whereby multipurpose: Ihanced inefletiveness prepared" Because'of-their havingsuchfprominent ifas mentioned above, the insecticidal compositiqnso the present 7invention; find} widefor the, preventionv of epidemics by injurious asfhou'se'flies, mosquitoes andcockr'oaches,

" control-of common mites, lndianrneal-rnoths, rice '1 weevils and thelike-insects injurious 'to stored cereals.

I Furthermore, they are markedly effectivenot 0519 .for. the control ofagriculture,horticultureand forestry injurious insectssuch as'planthoppers, leafhoppers, stem 4' fe th borers, diamond-back moths,i,l eaf rolle'rs,-, s ider mites and chestnut? caterpillars, but-'-alsofor the control of lice'and'ticks'parasitic to and'many other injuriousinsects. The compositions of present invention are particularly lowin'toxicity and hence are excellent alsoin that they can freely appliedto crops before harvest and to packaging for foods, 7

and are safely usable -for home horticulture andgreenhouse cultivation.

Formulation procedures and effects of the present compositions areillustrated below with reference to Formulation Examples and TestExamples, inwhich all parts are by weight.

FORMULATION EXAMPLE 1 Y A mixture comprising 0.06 part of (i)-cis,-transbody of the compound (1) 0.04 part of (id-trans body of the compound (3)was dissolved iii-deodorized kerosene to make thetotal amount parts,whereby an oil preparation was obtained. I

FORMULATION EXAMPLEIZ A mixture comprising 0.04 part of (+)-cis",transbody of the compound (1) and 0.01 part of (i)-trans body of the compound(3) was charged with 0.25 part of piperonyl butoxide and then dissolvedin deodorized kerosene to make the total amount 100 parts, whereby anoil preparation was obtained.

FORMULATION EXAMPLE 3 A mixture comprising 4 parts of (i)-cis,trans bodyof the compound l) and 16 parts of (i)-cis,trans body of the compound(3) was sufficiently stirred together with 15 parts of Sorpol SM-200(registered trademark of Toho Chemical Co.) and 65 parts of xylene,whereby an emulsifiable concentrate was obtained.

FORMULATION EXAMPLE 4 FORMULATION EXAMPLE 5 A mixture comprising 0.2part of (+)-trans body of the compound (1), 0.1 part of (i)-trans bodyof the compound (3), 13.7 parts of deodorized kerosene and 1 part of anemulsifier Atmos 300 (registered trademark of Atlas Chemical Co.) wasemulsified by addition of 50 parts of pure water. The resulting emulsionwas charged, together with a 3:1 mixture of deodorized butane anddeodorized propane, into an aerosol container to obtain a water-basedaerosol preparation.

FORMULATION EXAMPLE 6 A mixture comprising 0.1 g of (+)-cis,trans bodyof the compound (1), 0.3 g of (:)-trans body of the compound (3) and 0.4g of BHT was dissolved in 20 ml. of methanol, and then uniformly mixedunder stirring with 99.2 g of a mosquito coil carrier (a 3:5:1 mixtureof Tabu powder, pyrethrum marc and wood flour). The resulting mixture,after evaporation of methanol, was sufficiently kneaded with 150 ml. ofwater, and then shaped and dried to obtain a mosquito coil.

FORMULATION EXAMPLE 7 A mixture comprising 10 parts of (i)-cis,transbody of the compound 1 20 parts of (1)-cis,trans body of the compound(3) and parts of Sorpol SM-200 (same as mentioned previously) wassufficiently stirred in a mortar together with 65 parts of 300-mesh talcto obtain a wettable powder.

FORMULATION EXAMPLE 8 A mixture comprising 2 parts of (+)-trans body ofthe compound (1 1 part of (:)-trans body of the compound (3) and partsof piperonyl butoxide was dissolved in 20 parts of acetone, andsufficiently stirred in a mortar together with 87 parts of 300-meshdiatomaceous earth. Thereafter, acetone was removed by evaporation toobtain a dust preparation.

FORMULATION EXAMPLE 9 A mixture comprising 2 parts of (1)-cis,trans bodyof the compound (1) and 2 parts of (i)-trans or (i) cis,trans body ofthe compound (3) was sufficiently stirred in a mortar together with 5parts of Toyolignin CT (registered trademark of Toyo Spinning Co.) and91 parts of GSM Clay (registered trademark of Zieklite Kogyo Co.). Theresulting mixture was kneaded with 10% by weight based on the weight ofthe mixture of water, granulated by means of a granulator and thenair-dried to obtain fine granule preparations of the respective compoundmixtures.

FORMULATION EXAMPLE 10 A mixture comprising 0.06 part of (+)-lon-(+)-cis,trans body of the compound (2) and 0.04 part of (:t)-trans body ofthe compound (3) was dissolved in deodorized kerosene to make the totalamount 100 parts, whereby an oil preparation was obtained.

FORMULATION EXAMPLE 1 1 A mixture comprising 0.04 part of(+)-lon-(+)-trans body of the compound (2) and 0.01 part of (i)-cis,trans body of the compound (3) was charged with 0.25 part ofpiperonyl butoxide and then dissolved in deodorized kerosene to make thetotal amount 100 parts, whereby an oil preparation was obtained.

FORMULATION EXAMPLE 12 A mixture comprising 4 parts of(i)-lon-(i)-cis,trans body of the compound (2) and 16 parts of(i)-cis,trans body of the compound (3) was charged with parts of SorpolSM-ZOO and 65 parts of xylene, and the resulting mixture wassufficiently stirred to obtain an emulsifiable concentrate.

FORMULATION EXAMPLE 13 A mixture comprising 0.2 part of (i)-lon-(+)-cis,trans body of the compound (2), 0.1 part of (+)-trans body of thecompound (3), 7 parts of xylene and 7.7 parts of deodorized kerosene wascharged in an aerosol container. After attaching a valve portion to thecontainer, parts of a propellant (liquefied petroleum gas) was filledunder pressure through said valve portion into the container to obtainan aerosol preparation.

FORMULATION EXAMPLE 14 A mixture comprising 0.2 part of(+)-lon-(+)-trans body of the compound (2), 0.1 part of (i)-cis,transbody of the compound (3), 13.7 parts of deodorized kerosene and 1 partof an emulsifier Atmos 300 (same as mentioned previously) was emulsifiedby addition of 50 parts of pure water. The resulting emulsion wascharged, together with a 3:1 mixture of deodorized butane and deodorizedpropane, into an aerosol container to obtain a water-based aerosolpreparation.

FORMULATION EXAMPLE 15 A mixture comprising 0.1 g of(i)-lon-(i)-cis,trans body of the compound (2), 0.3 g of (+)-cis,transbody of the compound (3) and 0.4 g of BI-IT was dissolved in 20 ml ofmethanol, and then uniformly mixed under stirring with 99.2 g of amosquito coil carrier (a 3:5:1 mixture of Tabu powder, pyrethrum mareand wood flour). The resulting mixture, after evaporation of methanol,was sufficiently kneaded with ml of water, and then shaped and dried toobtain a mosquito coil.

FORMULATION EXAMPLE 16 A mixture comprising 0.02 g of (i)-lon-(+)-transbody of the compound (2) and 0.05 g of (2)-cis,trans body or 0.03 g(+)-trans body of the compound (3) was charged with 0.05 g of BHT and0.1 g of piperonyl butoxide. The resulting mixture was dissolved in aproper amount of chloroform, and uniformly adsorbed in a filter paper of3.5 cm X 1.5 cm in area and 0.3 cm in thickness to obtain fibrousfumigant compositions of the respective compound mixtures which were tobe used by heating on an electrically heated plate.

In addition to the filter paper, there may be used any fibrous carrierssuch as pulp and asbestos plates, which are equivalent in effectivenessto the filter paper, to obtain various fumigant compositions of thistype.

FORMULATION EXAMPLE 17 A mixture comprising 10 parts of (i)-lon-(+)-cis,trans body of the compound (2), 20 parts of (i)- cis,trans body ofthe compound (3) and 5 parts of Sorpol SM-200 (same as mentionedpreviously) in a mortar together with 65 parts of 300-mesh talc toobtain a wettable powder.

FORMULATION EXAMPLE 1 8 A mixture comprising 2 parts of(i)-lon-(+)-trans body of the compound (2), 1 part of (i)-trans body ofthe compound (3) and 10 parts of piperonyl butoxide was dissolved in 20parts of acetone, and sufficiently stirred in a mortar together with 87parts of 300-mesh diatomaceous earth. Thereafter, acetone was removed byevaporation to obtain a dust preparation.

FORMULATION EXAMPLE 19 A mixture comprising 2 parts of (+)-lon-(+)-transbody of the compound (2) and 2 parts of (+)-trans or (+)-cis,trans bodyof the compound (3) was sufficiently stirred in a mortar together with 5parts of Toyolignin CT (same as mentioned previously) and 91 parts ofGSM Clay (same as mentioned previously). The resulting mixture waskneaded with 10% by weight based on the weight of the mixture of water,granulated by means of a granulator and then air-dried to obtain finegranule preparations of the respective compound mixtures.

Insecticidal effects of the present compositions obtained in the abovemanner are as described in the following Test Examples.

TEST EXAMPLE 1 About 50 housfly adults were released in a glass chamberof (70 cm) and sprayed with 0.7 ml of each of the oil preparationsobtained in Formulation Examples l, 2 and 10 under a pressure of 1.5kg/cm by use of a glass atomizer, whereby more than 80% of the fliescould be knocked down within 10 minutes.

TEST EXAMPLE 2 According to the Campbells turn table method [Soap &Sanitary Chemicals, Vol. 14, No. 6, page 1 19 (1938)], 5 ml of each ofthe oil preparations obtained in Formulation Examples 1, 2, l and ll wassprayed, and a group of about 100 housefly adults was exposed to thedescending mist for l0 minutes. As the result, the death of more than80% of the flies could be observed on the next day.

TEST EXAMPLE 3 Each of the emulsifiable concentrates obtained inFormulation Examples 3 and 12 was diluted with water to form a20,000-fold dilution. 2 Liters of the dilution was charged in a styrenecase of 23 cm in width, 30 cm in length and 6 cm in depth, and about 100last-instar larvae of Northern house mosquitoes were liberated in thecase. As the result, the death of more than 90% of the larvae could beobserved on the next day.

TEST EXAMPLE 4 Rice plants, elapsed 45 days after sowing, were grown inl/50,000 Wagner pots, and sprayed with 10 ml/pot of an aqueous 500-folddilution of each of the emulsifiable concentrates obtained inFormulation Examples 3 and 12. Subsequently, each pot was covered with awire net, and about 30 adults of green rice leafhoppers were liberatedin the net. As the result, the death of more than 90% of the leafhopperscould be observed on the next day.

TEST EXAMPLE In a glass Petri dish of 14 cm in diameter were put tobaccocutworm larvae at the third to forth instar stage, and 1 ml. of anaqueous ZOO-fold dilution of each of the emulsifiable concentratesobtained in Formulation Examples 3 and 12 to the larvae by use of aspraying tower.

Thereafter, the larvae were transferred to another Petri dish withbaits. As the result, the death of more than 90% of the cutworm larvaecould be observed on the next day.

TEsT EXAMPLE 6 Insecticidal effectson housefly adults of the aerosolpreparations obtained in Formulation Examples 4, 5, l3 and 14 weretested according to the aerosol test method [described in Soap &Chemical Specialities, Bluebook (1965)] using a Peet Gradys chamber (6ft) As the result, all the aerosol preparations could knock down morethan 80% of the flies within 15 minutes after the spraying and couldbring more than of the flies to death on the next day.

TEST EXAMPLE 7 About 50 adults of Northern house mosquitoes werereleased in a glass chamber of (70 cm), and a small electric fan of 13cm in diameter equipped in the chamber was put in motion. Subsequently,0.1 g of each of the mosquito coils obtained in Formulation Examples 6and 15 was ignited on one end and placed at the center of the chamberbottom. As the result, all the mosquito coils could knock down more than90% of the mosquitoes and could bring more than thereof to death on thenext day.

TEST EXAMPLE 8 About 50 houseflies were released in a glass chamber of(70 cm), and a small electric fan (13 cm in diameter) equipped in thechamber was put in motion. Subsequently, the heating fumigantcomposition obtained in Formulation Example 16 was placed on anelectrically heated plate and fumigated in the chamber. As the result,more than of the houseflies could be knocked down within 20 minutes.

TEST EXAMPLE 9 vEach of the dust preparations obtained in FormulationExamples 9 and 18 was uniformly sprinkled in a proportion of 2 g/m onthe bottom of a Petri dish of 14 cm in diameter, and then butter wascoated on the inner wall of the dish, except the portion of l cm'fromthe bottom. Subsequently, a group of 10 adult German cockroaches wasliberated in the dish and contacted with the dust preparation for 30minutes, whereby more than 90% of knocked down cockroaches could bekilled during 3 days after the contact.

TEST EXAMPLE l0 Into 10 liters of water in a 14-liter polyethylene-madepail was charged 1 g of each of the granule preparations obtained inFormulation Examples 9 and 19. After one day, about last-instar larvaeof Northern house mosquitoes were liberated in said water, and the aliveand dead of the larvae were observed with time. As the result, more than90% of the larvae could be killed within 24 hours.

TEST EXAMPLE 1 l 3 Grams of each of the oil preparations obtained inFormulation Examples 2 and 1 1 was fogged by means of an insect fogger(manufactured by Burgess Vibrocrafters, lnc., U.S.A.) into the same PeetGradys chamber as in Test Example 6 into which about 500 houseflies hadpreviously been released. As the result, more than 90% of the housefliescould be knocked down within 30 minutes.

TEST EXAMPLE 12 Chinese cabbages were grown in a green house, and wereartificially parasitized with cutworms, cabbage worms and diamond-backmoths. Thereafter, the green house (2 m in height) was divided intocompartments of (30 m in area, and each compartment was fumigated by useof a thermofumigator (SEARCH) with g of each of the wettable powdersobtained in Formulation Examples 7 and 17. As the result, no increasingdamage of the cabbages was substantially observed.

TEST EXAMPLE 1 3 Mottled kidney bean plants (at the stage of 2-leaves),which had elapsed 9 days after sowing in flower pots, were parasitizedwith 10 to female carmine mites per leaf, and then allowed to stand fora week in a thermostat at 27C, whereby the mites at various growthstages propagated in large numbers. At this stage, an aqueous ZOO-folddilution-of each of the emulsifiable concentrates obtained inFormulation Examples 3 and 12 was sprayed to the plants in a proportionof 10 ml per pot, using a turn table. After 10 days, the plants wereexamined to find no substantial damage.

TEST EXAMPLE 14 An aqueous lOO-fold dilution of each of the wettablepowders obtained in Formulation Examples 7 and 17 was applied in aproportion of 50 ml/m onto the surface of a plywood of 15 cm X 15 cm inarea. On the other hand, a group of 20 adults of Northern housemosquitoes was released in a Petri dish of 9 cm in diameter. This dishwas placed upside down on the plywood surface treated with the saidchemical to contact the mosqitoes with the treated surface and, after 60minutes, the number of knocked down mosquitoes was counted.

In the above manner, the chemical applied to the plywood surface wasexamined in knock-down effect on the day of application and thereafteronce a week. As the result, the chemical showed a knockdown effect ofmore than even after 4 weeks had elapsed from the day of application tothe plywood surface, and thus was excellent in residual effect.

What we claim is:

1. An insecticidal composition containing an inert carrier and as activeingredients an insecticidally effective amount of a mixture consistingof (1) N-(3,4,5,6- tetrahydrophthalimido)-methyl chrysanthemate or (2)2-allyl-3-methyl-cyclopent-2-enel -one-4-yl chrysanthemate and (3)3-phenoxybenzyl-2',2'-dimethyl-3'- (2 ,2 -dichlorovinyl)cyclopropanecarboxylate wherein the ratio of compounds (1) or (2) tocompound (3) is 2:8 to 8:2.

2. The insecticidal composition according to claim 1, wherein saidcomposition contains 0.05 to by weight of the active ingredients.

3. The insecticidal composition according to claim 1, wherein themixture consists of compound (1 and compound (3).

4. The insecticidal composition according to claim 1, wherein themixture consists of compound (2) and compound (3).

5. The insecticidal composition according to claim 4, wherein compound(2) is (i)-2-allyl-3-methyl-cyclopent-Z-enel -one-4-yl(+)-trans-chrysanthemate.

6. The insecticidal composition according to claim 4, wherein compound(2) is (+)-2-allyl-3-methyl-cyclopent-2-ene- 1-one-4-yl(+)-trans-chrysanthemate.

7. The insecticidal composition according to claim 1, wherein compound(3) is 3-phenoxybenzyl-(i)- cis,trans-2 ',2-dimethy1-3 2 ,2''-dichlorovinyl) cyclopropanecarboxylate.

8. The insecticidal composition according to claim 1, wherein compound(3) is 3-phenoxybenzyl-(+)-trans- 2' ,2 -dimethyl-3 -(2 ,2-dichlorovinyl) cyclopropanecarboxylate.

9. A method for knocking down and killing insects, which comprisescontacting the insects with an insecticidally effective amount of thecomposition of claim 1.

1. AN INSECTICIDAL COMPOSITION CONTAINING AN INERT CARRIER AND AS ACTIVEINGRIEDIENTS AN INSECTICIDALLY EFFECTIVE AMOUNT OFF A MIXTURE CONSISTINGOF (1) N-(3,4,5,6-TETRAHYDROPHTHALIMIDO)-METHYL CHRYSANTHEMATE OR (2)2-ALLYL-3-METHYLCYCLOPENT-2-ENE-1-ONE-4-YL CHRYSANTHEMATE AND (3)3PHENOXYBENZYL-2'',2''-DIMETHYL-3''-(2",2"-DICHLOROVINYL)CYCLOPROPANECARBOXYLATE WHEREIN THE RATIO COMPOUNDS (1) OR (2) TOCOMPOUND (3) IS 2:8 TO 8:2.
 2. The insecticidal composition according toclaim 1, wherein said composition contains 0.05 to 90% by weight of theactive ingredients.
 3. The insecticidal composition according to claim1, wherein the mixture consists of compound (1) and compound (3).
 4. Theinsecticidal composition according to claim 1, wherein the mixtureconsists of compound (2) and compound (3).
 5. The insecticidalcomposition according to claim 4, wherein compound (2) is ( + or -)-2-allyl-3-methyl-cyclopent-2-ene-1-one-4-yl (+)-trans-chrysanthemate.6. The insecticidal composition according to claim 4, wherein compound(2) is (+)-2-allyl-3-methyl-cyclopent-2-ene-1-one-4-yl(+)-trans-chrysanthemate.
 7. The insecticidal composition according toclaim 1, wherein compound (3) is 3-phenoxybenzyl-( + or -)-cis,trans-2'',2''-dimethyl-3''-(2'''',2''''-dichlorovinyl)cyclopropanecarboxylate.
 8. The insecticidal composition according toclaim 1, wherein compound (3) is3-phenoxybenzyl-(+)-trans-2'',2''-dimethyl-3''-(2'''',2''''-dichlorovinyl) cyclopropanecarboxylate.
 9. A method for knockingdown and killing insects, which comprises contacting the insects with aninsecticidally effective amount of the composition of claim 1.